Suzuki-Miyaura Carbonylative Reaction in the Synthesis of Biaryl Ketones

Palladium-catalyzed carbonylative coupling reactions of aromatic halides and aryl boronic acids have been rapidly developed during recent years. Nowadays, a plethora of boronic acid compounds, palladium catalyst precursors and CO resources are available for the synthesis of diaryl ketones, which are important intermediates in the manufacture of dyes, pharmaceuticals and natural products. In this review, we summarize the development of these carbonylative reactions with aspects of palladium catalyst system, transmetallation, alternative CO resources and application. The progress on palladium catalyst system covers both homogeneous and heterogeneous reaction systems. A large variety of palladium catalyst precursors, phosphine ligands, HNC ligands in different solvents are discussed in detail, whilst palladium catalysts immobilized on active carbon, graphene, ligand functionalized silica gel, Fe3O4 are also included. Notably, the improvement in the transmetallation process is potentially valuable of achieving efficient carbonylative coupling reaction, in which the pivalic acid additive is found to accelerate the carbonylative coupling. In the classic carbonylative procedure, CO gas from high pressurized cylinders is required in palladium catalyzed Suzuki carbonylative reaction. Although few innovations using CO balloon is reported, the replace of odorless and toxic CO gas by carbon monoxide release molecules (CORM) are highly desirable and offered a safer and greener carbonylation process. To supply CO for palladium-catalyzed carbonylative coupling reaction, various organic CORMs releases CO via controllable degradation in two-chamber system. Transition metal carbonyl compounds as solid CORM directly provides CO under microwave radiation.